CN109830706A - A kind of electrode frame structure and the zinc-bromine flow battery with its assembling - Google Patents
A kind of electrode frame structure and the zinc-bromine flow battery with its assembling Download PDFInfo
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- CN109830706A CN109830706A CN201711182518.1A CN201711182518A CN109830706A CN 109830706 A CN109830706 A CN 109830706A CN 201711182518 A CN201711182518 A CN 201711182518A CN 109830706 A CN109830706 A CN 109830706A
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- China
- Prior art keywords
- electrode frame
- battery
- plate
- hole
- electrode
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- ZRXYMHTYEQQBLN-UHFFFAOYSA-N [Br].[Zn] Chemical compound [Br].[Zn] ZRXYMHTYEQQBLN-UHFFFAOYSA-N 0.000 title claims description 11
- 239000012528 membrane Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 6
- 229920001971 elastomer Polymers 0.000 claims description 4
- 238000012856 packing Methods 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052794 bromium Inorganic materials 0.000 abstract description 23
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 21
- 239000000126 substance Substances 0.000 abstract description 14
- 239000007788 liquid Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- VNDYJBBGRKZCSX-UHFFFAOYSA-L Zinc bromide Inorganic materials Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000008595 infiltration Effects 0.000 description 6
- 238000001764 infiltration Methods 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000008139 complexing agent Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229940102001 zinc bromide Drugs 0.000 description 2
- 229920001342 Bakelite® Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Hybrid Cells (AREA)
Abstract
The present invention relates to a kind of electrode frame structures, electrode frame is the plate-like structure that middle part has through-hole, cavity of the middle part hollowed out area as accommodating electrode where through-hole, the edge of one side surface of electrode frame plate is provided with annular seal groove, offers annular groove to the direction far from through-hole in the edge of one side surface through-hole of electrode frame.On the one hand the invention reduces positive gasket, reduce costs.More importantly diaphragm is entirely sealed in electrode frame, it is exposed to from traditional diaphragm section different in external environment, has thoroughly prevented the problem of bromine simple substance is permeated by diaphragm section.
Description
Technical field
The present invention relates to a kind of electrode frame structure and the zinc-bromine flow batteries assembled with it.
Background technique
Zinc-bromine flow battery has the advantages that high-energy density, low cost compared to all-vanadium flow battery.Zinc bromine liquid energy-storage
Battery theoretical open circuit voltage 1.80V or so, theoretical energy density 430Wh/kg.Zinc-bromine flow battery positive and negative anodes are separated by diaphragm,
Two sides electrolyte solution is ZnBr2Solution.Under the action of kinetic pump, electrolyte solution is closed what fluid reservoir and battery were constituted
It closes and is circulated in circuit.Potential difference between positive and negative anodes electrode pair is the power to react, zinc-bromine flow battery
Electrode reaction are as follows:
Anode:(E θ=1.076V)
Cathode:(E θ=- 0.76V)
The research of zinc-bromine flow battery starts from beginning of the eighties late 1970s.Zinc-bromine flow battery the U.S. develop compared with
Fastly, ZBB company in the U.S. provides a variety of commercialization modules such as 50kWh and 500kWh and apply and shows for 2008 to potential customers
Model, and zinc bromine liquid flow energy storage battery is positioned at the fields such as electric vehicle power sources, wind and solar energy energy-storage battery, emergency power supply.
Nevertheless, zinc-bromine flow battery will reach industrial application, there are still many problems and challenge to need further
It solves.
Anode bromine simple substance environment friendly problem.The bromine environmental pollution and infiltration of anode are to restrict zinc bromine liquid stream
The critical issue of battery functionization and industrialization.When battery charges the bromine simple substance that generates can not discharge regime become completely bromine from
On the one hand son causes the battery coulombic efficiency of following cycle to decline, is on the one hand easy to cause positive bromine elemental concentration excessively high, infiltration
It is polluted into environment., molten in electrolyte to reduce such self discharge and environmental pollution, existing solution is: 1)
Bromine simple substance complexing agent is added in liquid, reduces the bromine elemental concentration of free state.Common bromine simple substance complexing agent is mainly that bromination is water-soluble
Property organic compound, by complexing agent be complexed bromine simple substance it is independent at phase the characteristics of, reduce free state bromine simple substance in electrolyte solution
Content solves bromine simple substance infiltration problem；2), by developing cheap resistance bromine diaphragm, on the basis of guaranteeing ionic conduction, regulation
Bromine membrane thicknesses and pore-size distribution are hindered to realize the isolation of positive and negative electrode electrolyte solution, reduce the infiltration of bromine.
But in fact, the infiltration of reply bromine simple substance at present and etching problem are still without preferably method.Therefore, in electricity
When pond group assembles, need using the gasket of the materials such as PP, PE to prevent bromine simple substance from leaking out.Moreover, comparing full vanadium liquid
The sealing difficulty of galvanic battery, bromine simple substance is bigger, because its form that gaseous volatilization is presented, is easy to by porous septum
Portion's horizontal infiltration is to outside.
Summary of the invention
The present invention proposes for the sealing problem of zinc-bromine flow battery anode bromine simple substance and utilizes PP, PE diaphragm itself
Telescopicing performance is provided with annular groove in electrode frame, gets rid of traditional diaphragm, gasket, electrode frame three successively contact
Form is changed in the annular groove that diaphragm is directly placed into the electrode frame with annular groove, by adjusting annular groove depth
Sealing effect is realized in subsequent be closely assembled with the thickness of diaphragm.On the one hand the invention reduces positive gasket, reduce
Cost.More importantly diaphragm is entirely sealed in electrode frame, it is exposed in external environment with traditional diaphragm section
Difference has thoroughly prevented the problem of bromine simple substance is permeated by diaphragm section.
The purpose of the invention is achieved by the following technical solution:
A kind of electrode frame structure, electrode frame are the plate-like structure that middle part has through-hole, the middle part vacancy section where through-hole
Cavity of the domain as accommodating electrode, the edge of one side surface of electrode frame plate is provided with annular seal groove, in electrode frame
The edge of one side surface through-hole offers annular groove to the direction far from through-hole.
Annular groove is between sealed groove and plate middle through-hole；The depth of annular groove is less than membrane thicknesses.
Battery includes the folded positive end plate of sequential layer, anode collection plate, electrode frame of the present invention, anode, diaphragm, bears
Pole, cyclic sealing gasket, negative electrode frame, negative pole currect collecting plate, negative end plate.
The electrode frame annular recess is thick in the diaphragm that the depth of plate level to annular groove bottom surface is 80-90%
Degree.
The diaphragm is the porous or dense membrane of PP or PE material.
The diaphragm is rectangle, and length and wide size dimension are less than or equal to the length and width ruler of rectangle annular groove
It is very little, it is greater than rectangular through holes length and width dimensions.
The membrane thicknesses are 100-1000 microns.
Gask-O-Seal can be used acidproof sheet rubber or use acidproof rubber covered wire.
Electrode uses graphite felt or carbon felt, or can also use carbon paper；Collector plate is metal or carbon materials lumber；Electrode
Framework material is polyethylene, polypropylene, polyvinyl chloride or ABS；The end plate material can be larger for rigidity such as aluminium or stainless steels
Metal material or bakelite plate or plastic plate.
Sealed groove is 1-5mm, width 5-10mm relative to the depth of plate level.
Detailed description of the invention
Fig. 1, the electrode frame front view with annular groove；1- annular groove；2- sealed groove；3- through-hole
The assembling schematic diagram of Fig. 2, the electrode frame with annular groove and electrode, gasket；
Wherein 1- cathode carbon felt；2- anode carbon felt；3- diaphragm；4- gasket；5- has the anode electrode frame of annular groove；
6- negative electrode frame
Fig. 3, traditional electrode frame front view；
The assembling schematic diagram of Fig. 4, traditional electrode frame and gasket, electrode, gasket.
Wherein: 1- cathode carbon felt；2- anode carbon felt；3- diaphragm；4- gasket；5- gasket；6- anode electrode frame；7- is negative
Pole electrode frame
Specific embodiment
Embodiment 1
By taking the pile of electrode frame proposed by the present invention (Fig. 1,2 shown in) assembling as an example, assembled by 10 section monocells,
Circuit connection, electrode area 875cm are carried out using bipolar plates between every batteries2, using 500 μm of PP perforated membranes, annular groove
450 μm of depth.Electrolyte is 2.0mol/L zinc bromide, and charging and discharging currents density is 40mA/cm2, charging time 1h；Positive electricity
The volume for solving liquid and electrolyte liquid is 20L.
Battery pack coulombic efficiency 97%, voltage efficiency 84%, energy efficiency 81%.Coulomb individual pen rate of decay 0.001%.
Comparative example
Using electrode frame shown in Fig. 3,4, mutually isostructural pile is assembled using material identical as embodiment, by 10
Section monocell assembles, and carries out circuit connection, electrode area 875cm using bipolar plates between every batteries2, using 500 μ
MPP perforated membrane, electrolyte are 2.0mol/L zinc bromide, and charging and discharging currents density is 40mA/cm2, charging time 1h；Positive electricity
The volume for solving liquid and electrolyte liquid is 20L.
Battery pack coulombic efficiency 95%, voltage efficiency 82%, energy efficiency 78%.Coulomb individual pen rate of decay 0.01%.
As can be seen that the battery pack of electrode frame and assembling of the invention has higher coulombic efficiency from battery performance.
More importantly since the electrode frame of invention prevents bromine simple substance, to exosmosis, to ensure that battery pack by diaphragm
Coulombic efficiency keeps stablizing, the substantially unattenuated battery pack compared to the assembling of traditional electrode frame.
Claims (8)
1. a kind of electrode frame structure, electrode frame is the plate-like structure that middle part has through-hole, the middle part hollowed out area where through-hole
As the cavity of accommodating electrode, the edge of one side surface of electrode frame plate is provided with annular seal groove, it is characterised in that:
Annular groove is offered to the direction far from through-hole in the edge of one side surface through-hole of electrode frame.
2. electrode frame structure as described in claim 1, it is characterised in that: annular groove is in logical in the middle part of sealed groove and plate
Between hole；The depth of annular groove is less than membrane thicknesses.
3. a kind of zinc-bromine flow battery assembled using electrode frame structure as claimed in claim 1 or 2, it is characterised in that: battery pack
Positive end plate, anode collection plate, electrode frame as claimed in claim 1 or 2, anode, diaphragm, cathode, the ring-type for including sequence stacking are close
Packing, negative electrode frame, negative pole currect collecting plate, negative end plate.
4. battery as claimed in claim 3, it is characterised in that: electrode frame annular recess as claimed in claim 1 or 2 is in plate
The membrane thicknesses that the depth of plane to annular groove bottom surface is 80-90%.
5. battery as claimed in claim 3, it is characterised in that: the diaphragm be PP or PE material it is porous or fine and close every
Film.
6. battery as claimed in claim 3, it is characterised in that: the diaphragm is rectangle, length and wide size dimension
Less than or equal to the length and width dimensions of rectangle annular groove, it is greater than rectangular through holes length and width dimensions.
7. battery as described in claim 3 or 4, it is characterised in that: the membrane thicknesses are 100-1000 μm.
8. battery as claimed in claim 3, it is characterised in that: Gask-O-Seal can be used acidproof sheet rubber or using acidproof
Rubber covered wire.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711182518.1A CN109830706B (en) | 2017-11-23 | Electrode frame structure and zinc-bromine flow battery assembled by same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711182518.1A CN109830706B (en) | 2017-11-23 | Electrode frame structure and zinc-bromine flow battery assembled by same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109830706A true CN109830706A (en) | 2019-05-31 |
| CN109830706B CN109830706B (en) | 2024-10-01 |
Family
ID=
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113036170A (en) * | 2019-12-09 | 2021-06-25 | 中国科学院大连化学物理研究所 | Zinc-bromine battery |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0439873A (en) * | 1990-06-04 | 1992-02-10 | Meidensha Corp | Zinc-bromine battery |
| CN102456905A (en) * | 2010-10-27 | 2012-05-16 | 新奥科技发展有限公司 | Liquid flow battery unit, battery stack and manufacturing method thereof |
| CN102569843A (en) * | 2012-01-13 | 2012-07-11 | 清华大学 | Embedded electrode frame of flow cell pile |
| CN103840180A (en) * | 2012-11-23 | 2014-06-04 | 中国科学院大连化学物理研究所 | Flow cell wire sealing structure with self-locating function |
| CN103840188A (en) * | 2012-11-23 | 2014-06-04 | 中国科学院大连化学物理研究所 | Flow battery stack structure |
| CN207441864U (en) * | 2017-11-23 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of zinc-bromine flow battery electrode frame structure and include its flow battery |
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0439873A (en) * | 1990-06-04 | 1992-02-10 | Meidensha Corp | Zinc-bromine battery |
| CN102456905A (en) * | 2010-10-27 | 2012-05-16 | 新奥科技发展有限公司 | Liquid flow battery unit, battery stack and manufacturing method thereof |
| CN102569843A (en) * | 2012-01-13 | 2012-07-11 | 清华大学 | Embedded electrode frame of flow cell pile |
| CN103840180A (en) * | 2012-11-23 | 2014-06-04 | 中国科学院大连化学物理研究所 | Flow cell wire sealing structure with self-locating function |
| CN103840188A (en) * | 2012-11-23 | 2014-06-04 | 中国科学院大连化学物理研究所 | Flow battery stack structure |
| CN207441864U (en) * | 2017-11-23 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of zinc-bromine flow battery electrode frame structure and include its flow battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113036170A (en) * | 2019-12-09 | 2021-06-25 | 中国科学院大连化学物理研究所 | Zinc-bromine battery |
| CN113036170B (en) * | 2019-12-09 | 2022-02-11 | 中国科学院大连化学物理研究所 | Zinc-bromine battery |
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